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Title: Semi-volatile and highly oxygenated gaseous and particulate organic compounds observed above a boreal forest canopy

Abstract

We present hourly online observations of molecular compositions (C xH yO zN 0-1) and abundances of oxygenated organic species in gas and submicron particle phases from April to June of 2014 as part of the Biogenic Aerosols-Effects on Cloud and Climate (BAECC) campaign. Measurements were made using the Filter Inlet for Gases and AEROsols coupled to a high-resolution time-of-flight iodide-adduct ionization mass spectrometer (FIGAERO-CIMS) located atop a 35m tall tower, about 10m above a boreal forest canopy at the SMEAR II research station in Hyytiälä, Finland. Semi-volatile and highly oxygenated multifunctional (HOM) organic species possessing from 1 up to 20 carbon atoms, and with as few as 2 and as many as 16 oxygen atoms, were routinely observed. Utilizing non-negative matrix factorization, we determined that >90 and >99% of the organic mass in the gas and particle phases, respectively, exhibited one of three distinct diel trends: one in which abundances were enhanced at daytime, another in the early morning hours, and thirdly during nighttime. Particulate organic nitrates contributed ~35% to the total organic aerosol mass loading at night during BAECC, much higher than observed by the same instrument package at a mixed-deciduous forest site in the southeastern US that experiencedmore » higher nighttime concentrations of nitrogen oxides. Unique HOM monomers (defined here as those with 10 carbon and 7 or more oxygen atoms) and dimers (at least 16 carbon atoms), with and without a nitrogen atom, were found in most of the three subgroups of both phases. We show the potential to connect these groupings of compounds based on their distinct behavior in time to the expected chemical conditions (biogenic VOC precursor, oxidant type, etc.) responsible for their production. A suite of nitrated dimer-like compounds was detected in both the gas and particle phases, suggesting a potential role for the formation of low-volatility organics from NO 3-radical-driven, as well as daytime NO-influenced, monoterpene chemistry.« less

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [3];  [3]; ORCiD logo [3];  [4];  [4];  [1]
  1. Univ. of Washington, Seattle, WA (United States). Dept. of Atmospheric Sciences
  2. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
  3. Univ. of Helsinki (Finland). Inst. for Atmospheric and Earth System Research/Physics. Faculty of Science
  4. Univ. of Eastern Finland, Kuopio (Finland). Dept. of Physics
Publication Date:
Research Org.:
Univ. of Washington, Seattle, WA (United States); Univ. of Helsinki (Finland); Univ. of Eastern Finland, Kuopio (Finland)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); Academy of Finland; Nordic Centre of Excellence
OSTI Identifier:
1502371
Grant/Contract Number:  
SC0006867; SC0018221; 307331; 57001
Resource Type:
Accepted Manuscript
Journal Name:
Atmospheric Chemistry and Physics (Online)
Additional Journal Information:
Journal Name: Atmospheric Chemistry and Physics (Online); Journal Volume: 18; Journal Issue: 15; Journal ID: ISSN 1680-7324
Publisher:
European Geosciences Union
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lee, Ben H., Lopez-Hilfiker, Felipe D., D'Ambro, Emma L., Zhou, Putian, Boy, Michael, Petäjä, Tuukka, Hao, Liqing, Virtanen, Annele, and Thornton, Joel A. Semi-volatile and highly oxygenated gaseous and particulate organic compounds observed above a boreal forest canopy. United States: N. p., 2018. Web. doi:10.5194/acp-18-11547-2018.
Lee, Ben H., Lopez-Hilfiker, Felipe D., D'Ambro, Emma L., Zhou, Putian, Boy, Michael, Petäjä, Tuukka, Hao, Liqing, Virtanen, Annele, & Thornton, Joel A. Semi-volatile and highly oxygenated gaseous and particulate organic compounds observed above a boreal forest canopy. United States. doi:10.5194/acp-18-11547-2018.
Lee, Ben H., Lopez-Hilfiker, Felipe D., D'Ambro, Emma L., Zhou, Putian, Boy, Michael, Petäjä, Tuukka, Hao, Liqing, Virtanen, Annele, and Thornton, Joel A. Wed . "Semi-volatile and highly oxygenated gaseous and particulate organic compounds observed above a boreal forest canopy". United States. doi:10.5194/acp-18-11547-2018. https://www.osti.gov/servlets/purl/1502371.
@article{osti_1502371,
title = {Semi-volatile and highly oxygenated gaseous and particulate organic compounds observed above a boreal forest canopy},
author = {Lee, Ben H. and Lopez-Hilfiker, Felipe D. and D'Ambro, Emma L. and Zhou, Putian and Boy, Michael and Petäjä, Tuukka and Hao, Liqing and Virtanen, Annele and Thornton, Joel A.},
abstractNote = {We present hourly online observations of molecular compositions (CxHyOzN0-1) and abundances of oxygenated organic species in gas and submicron particle phases from April to June of 2014 as part of the Biogenic Aerosols-Effects on Cloud and Climate (BAECC) campaign. Measurements were made using the Filter Inlet for Gases and AEROsols coupled to a high-resolution time-of-flight iodide-adduct ionization mass spectrometer (FIGAERO-CIMS) located atop a 35m tall tower, about 10m above a boreal forest canopy at the SMEAR II research station in Hyytiälä, Finland. Semi-volatile and highly oxygenated multifunctional (HOM) organic species possessing from 1 up to 20 carbon atoms, and with as few as 2 and as many as 16 oxygen atoms, were routinely observed. Utilizing non-negative matrix factorization, we determined that >90 and >99% of the organic mass in the gas and particle phases, respectively, exhibited one of three distinct diel trends: one in which abundances were enhanced at daytime, another in the early morning hours, and thirdly during nighttime. Particulate organic nitrates contributed ~35% to the total organic aerosol mass loading at night during BAECC, much higher than observed by the same instrument package at a mixed-deciduous forest site in the southeastern US that experienced higher nighttime concentrations of nitrogen oxides. Unique HOM monomers (defined here as those with 10 carbon and 7 or more oxygen atoms) and dimers (at least 16 carbon atoms), with and without a nitrogen atom, were found in most of the three subgroups of both phases. We show the potential to connect these groupings of compounds based on their distinct behavior in time to the expected chemical conditions (biogenic VOC precursor, oxidant type, etc.) responsible for their production. A suite of nitrated dimer-like compounds was detected in both the gas and particle phases, suggesting a potential role for the formation of low-volatility organics from NO3-radical-driven, as well as daytime NO-influenced, monoterpene chemistry.},
doi = {10.5194/acp-18-11547-2018},
journal = {Atmospheric Chemistry and Physics (Online)},
number = 15,
volume = 18,
place = {United States},
year = {2018},
month = {8}
}

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Cited by: 6 works
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Figures / Tables:

Figure 1 Figure 1: BAECC-median abundances of the organic nitrate (gold; ON=C$x$H$y$NO$z$) and organic carbon (blue; OC=C$x$H$y$N0O$z$) species in the (a) gas and (b) particle phases, plotted as a function of their molecular weights. The shaded green and blue areas in (a) and (b) highlight the molecular weight ranges of monoterpene-derived HOMmore » monomers (nC= 10 and nO≥ 7) and dimers (nC≥ 16). Sub-panels on the righthand side of (a) and (b) show the abundances of select monomers and dimers of the gas and particle phases, respectively.« less

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